DE1620975A1 - New copolymers, their manufacture and use - Google Patents

Description

PATENT LAWYERS

DR.-tNG. BY KREISLER DR.-ING. SCHÖNWALD DR.-ING. TH. MEYER DR. FUES DIPL.-CHEM. ALEK VON KREISLER DIPL-CHEM. CAROLA KELLER DR.-ING. KLDPSCH

COLOGNE 1, DEICHMANNHAUS 1620975

Cologne, January 26, 1970 Ke / Re

Montecatini Edison S, p.A.

, Foro Buonaparte, Milan (Italy)

New copolymers, their manufacture and uses.

The production of amorphous, vulcanizable copolymers of alkenylcycloalkenes, in particular, has already been carried out 4-vinyl-cyclohexene-l and l, 2-divinylcyclooctene-5i with monoolefins suggested. These copolymers are obtained with the aid of catalysts which, according to an anionic Coordination mechanisms work, especially with catalysts made from vanadium compounds and organometallic Compounds of aluminum and beryllium can be obtained.

According to the invention it has now been found that with these same catalysts is possible, linear, amorphous, unsaturated copolymers of one or more monoolefins, in particular ethylene and higher α-olefins, with one or more monoalkenylcyclobutenes, in particular with 3-methyl-4- (4-pentenyl) -cyclobutene, 3 (1-methylallyl) -cyclobutene and ^ - (5-hexenyl) -cyclobutene. These monomers can, for example, from decatriene-2,4,9, 5-methylheptatriene 1,3,6 and decatriene-1,3,9 by photoisomerization getting produced.

BATH

N * »Documents m.7giM ^ _ZHn OO9 * 20 / t # ft

As already mentioned, ethylene and / or aliphatic α-olefins of the general formula R-CH = CH ₃ , in which R is an alkyl radical having 1 to 6 carbon atoms, are copolymerized together with the dienes mentioned. Ethylene, propylene and butene-1 are preferably used as monoolefins.

The copolymers obtained from these monomers consist of unsaturated macromolecules with monomer units that originate from each of the monomers used. For example, by copolymerizing a mixture of Ethylene, propylene and / or butene-1 and j5-methyl-4 (4-pentenyl) -cyclobutene obtain a crude copolymerization product composed of macromolecules each of which in random distribution of monomer units of ethylene, Contains propylene and / or butene-1 and said diene.

Each monomer unit resulting from the polymerization of the diene contains a free multiple bond. This multiple bond represents a reactive site for subsequent reactions to which the copolymer can be subjected. This multiple bond enables, for example, the vulcanization of the copolymer with sulfur-containing mixtures of the type usually used for the vulcanization of unsaturated rubbers, preferably weakly unsaturated rubbers. The double bonds present in the macromolecules can also lead to the formation of polar groups, such as carbonyl groups, for example through oxidation with ozone. The carbonyl groups can represent reactive sites for subsequent reactions, for example vulcanization with polyvalent basic substances, and can be used to improve the adhesive properties of the copolymer. The double bonds can also; can be used in addition reactions with metal hydrides such as LiH, NaBH ^ or AIH (C ^ Hq) ₂ . The in this way

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formed metal-carbon bonds can in turn serve for subsequent reactions.

The new copolymers have an essentially linear structure. This is clearly indicated by the fact that they practically the same properties, especially that same viscosity behavior as known linear copolymers, for example the linear copolymers of ethylene with α-olefins. *

The viscosimetrically determined molecular weight of the new copolymer is about 20,000 in accordance with on the one in tetrahydronaphthalene at 1J55 ° C or in toluene at ⁰ C JO certain intrinsic viscosity of more than 0.5 * The intrinsic viscosity of the copolymers can be between 0,5 and 10 ', however, higher values can also be achieved. For most practical purposes, polymers with an intrinsic viscosity between 1 and 5 are preferred.

The composition of the copolymers can be described as practically homogeneous, the various monomer units being randomly distributed. Proof of the homogeneity of these copolymers is provided by the ability to normally get reindeer for the vulcanization of weak unsaturated "rubber types · such as butyl rubber, applied procedural _one good vulcanized products to the.

Evidence that the multiple bonds along the macromolecular chains of those produced according to the invention Copolymers are well distributed is the fact that, in contrast to the actual copolymers, which are in boiling n-heptane are completely soluble, the vulcanized products obtained therefrom in organic solvents such as aliphatic hydrocarbons, are completely insoluble and due to some aromatic solvents

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BAD ORlGiMAL

will.

medium can only be swollen to a limited extent.

The vulcanizates obtained show excellent mechanical strength and low deformation residues after Fracture. In particular, they have high reversible elastic elongations and high tensile strength, especially when used reinforcing fillers such as carbon black in the mixture.

The elastomers obtained by vulcanization can on Reason of their good mechanical properties for the production of a wide variety of objects, such as pipes, hoses, Foils, plates, rubber threads or seals are used

The new copolymers can by processes known per se be stretched or calibrated with hydrocarbon oils. For this purpose, paraffinic and naphthenic oils are used, but aromatic oils are also suitable.

The catalyst systems suitable for the preparation of the new copolymers are in the hydrocarbons, the can be used as a solvent for the copolymerization, for example in aliphatic, cycloaliphatic or aromatic hydrocarbons or their mixtures, highly dispersed or amorphous colloidal dispersed or completely dissolved and are made from organometallic compounds of beryllium or aluminum and made from vanadium compounds.

The following organometallic compounds, for example, can be used to prepare the catalysts be: beryllium dialkyls, beryllium alkyl halides, Beryllium diaryls, aluminum trialkyls, aluminum dialkyl monohalides; Aluminum monoalkyl dihalides, aluminum alkyl sesquihalides, aluminum alkylenes, aluminum alkenyls,

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Aluminum cycloalkyls, aluminum cycloalkyl alkyls, aluminum aryls, Aluminum alkylaryls, aluminum dialkylalkoxides, aluminum alkylalkoxyhalides, complexes of the above mentioned organoaluminum compounds with preferably weak Lewis bases *

As examples of compounds related to the above Group include: beryllium diethyl, beryllium methyl chlorine id, beryllium dimethyl, beryllium di-n-propyl, beryllium diisopropyl, beryllium di-n-butyl, beryllium di-t-butyl, - Beryllium diphenyl, AIu-

miniumtriethyl, aluminum triisobutyl, aluminum trihexyl, Aluminum diethyl monochloride, aluminum diethyl monofluoride, aluminum diisobutyl monochloride, aluminum monoethyl dichloride, Aluminum ethyl sesquichloride, aluminum butenyl diethyl, aluminum isohexenyl diethyl, 2-methyl-1,4-di (diisobutylaluminum) butane, Aluminum tri- (cyclopentylmethyl), Aluminum triidimethylcyclopentylmethyl), aluminum triphenyl, Aluminum tritolyl, aluminum di (cyclopentylmethyl) monochloride, Aluminum diisobutyl monochloride as a complex compound with anisole, aluminum monochloroethyl monoethoxide, Aluminum diethyl propoxide, aluminum diethyl amyloxide, aluminum monochloromonopropyl monopropoxide, aluminum monochloromonopropyl monoethoxide.

As already mentioned, vanadium compounds are used together with the aforementioned organometallic compounds in the preparation of the catalyst. Vanadium compounds are preferably used which are soluble in the hydrocarbons used as the polymerization medium, for example the halides and oxyhalides, such as VCIh, VOCl-, or VBr ₂ ,, and those compounds in which at least one metal valence occurs. a heteroatom bonded to an organic group, in particular oxygen or nitrogen, is saturated, for example vanadium triacetyiacetonate and -tr-ibenzoylace-

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^ß -AD ORIGINAL

I W L- U

tonate, vanadyl diacetylacetonate and haloacetylacetonate, Vanadyl trialkoxides and haloalkoxides, tetrahy- " drofuranate, a'therate, aminate, pyridinate and quinolinate of vanadium tri- and tetrachloride and of vanadyl trichloride.

Vanadium compounds from the group of organic salts that are insoluble in hydrocarbons, such as vanadium triacetate, -tribenzoate and -tristearate can also be used. For best results, the be carried out in practice in the presence of halogen-containing catalyst systems in which at least one component Contains halogen atoms.

The copolymerization can be carried out at temperatures from -80 ° to 125 ° C. In the case of catalysts made from vanadium triacetylacetonate, vanadyl diacetylacetonate or haloacetylacetonates or, more generally, from a vanadium compound such as VClj, or VOCl- ,, in addition to those mentioned above in the presence of aluminum alkyl halides, it is used to achieve high yields of copolymers per unit weight of the Appropriate catalyst, both the catalyst preparation and the copolymerization at temperatures between 0 ° and -80 ⁰ C, preferably between -10 ° and -50 ° C to carry out. When working under these conditions, the catalysts show a higher activity than catalyst systems which are produced at higher temperatures. Furthermore, the activity of the catalyst remains practically unchanged over time if the work is carried out within the above-mentioned range of low temperatures.

When catalysts composed of an aluminum alkyl halide and vanadium triacetylacetonate, vanadyl trialkoxides or haloalkoxides have been prepared at Tem-

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temperatures between 0 ° and 125 ° C are used to achieve high yields of copolymers expedient in the presence of special complexing agents, namely ethers, Thioethers, tertiary amines or trisubstituted phosphines, which contain at least one branched alkyl radical or an aromatic ring to work. The complexing agent can be an ether of the formula RYR ', in which Y is oxygen or sulfur and R and R' are linear

or branched alkyl radical with 1 to 14 carbon atoms or an aromatic ring with'to 14 carbon atoms, where at least one of the radicals R and R ^! is a branched alkyl radical or an aromatic ring.

The complexing agent can also be a tertiary amine of the formula

in which R, R ¹ and R "are alkyl radicals with 1 to 14 carbon atoms or aromatic rings with 6 to 14 carbon atoms and at least one of the radicals R is an aromatic ring.

The complexing agent can also be a tertiary phosphine formula

in which R, R ¹ and R "are alkyl radicals with 1 to 14 carbon atoms or aromatic rings with 6 to 14 carbon atoms and at least one of the radicals R is an aromatic ring.

The amount of the complexing agent is preferably 0.5 to 1 mole per mole of aluminum alkyl halide.

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BATH

The activity of the catalysts changes with the molar ratio between the compounds used to prepare them. It has been found that when using, for example, aluminum trialkyls and vanadium halides or oxyhalides, it is advisable to use catalysts in which the molar ratio of aluminum trialkyl to vanadium compound is between 1 and 5, preferably between 2 and 4, while when using aluminum diethyl monochloride (Al (CpH ₁ -) pCl) and vanadium triacetylacetonate (VAc.,) The best results can be obtained with a molar ratio of 2 to 20, preferably 4 to 10.

The copolymerization can take place in the presence of aliphatic, cycloaliphatic or aromatic hydrocarbons as a solvent, for example in the presence of butane, pentane, n-heptane, cyclohexane, benzene, toluene, xylene or their mixtures are carried out. Halogenated hydrocarbons such as methylene chloride, chloroform, trichlorethylene, Tetrachlorethylene or chlorobenzene can be used as solvents.

Particularly high polymerization rates can be achieved if the copolymerization is in the absence an inert solvent using the monomers themselves in the liquid state, i.e. in the presence of a Dissolution of the ethylene in the mixture of the α-olefins and the diene, which is kept in the liquid state, is carried out. However, it can be carried out in the absence of an inert solvent if only one of the in the alkenylcyclobutene Double bonds contained polymerized under the respective reaction conditions, for example if the double bond of the "'alkenyl radical internally or; is substituted. When both double bonds can react, networking takes place.

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In order to obtain very homogeneous copolymers, it is expedient to during the copolymerization the ratio between the concentrations of those in the reacting liquid phase to keep existing monomers to be polymerized constant or at least as constant as possible. For this purpose it can be advantageous to carry out the copolymerization continuously with a continuous feed and removal of a monomer mixture of constant Composition and to be carried out at high space air velocity. By changing the composition of the monomer mixture, the composition of the copolymer can be changed within wide limits.

When amorphous terpolymers of said polyenes with ethylene and propylene are desired, it is convenient to maintain the ethylene / propylene molar ratio in the reacting liquid phase below 1: 4 or at most 1: 4. This corresponds to an ethylene / propylene molar ratio in the gas phase of 1: 1 under normal conditions. Molar ratios in the liquid phase between 1: 200 and 1: 4 are usually preferred. When using butene-1 Instead of propylene, the ethylene / butene molar ratio must be less than or at most 1:20. This matches with an ethylene / butene-1 molar ratio in the gas phase of 1: 1.5 under normal conditions. Normally, molar ratios in the liquid phase are 1: 1000 up to 1:20 preferred.

When working under these conditions, amorphous terpolymers are obtained that are less than about Contains 75 moles of ethylene. If these values are exceeded, the terpolymer will have those for polyethylene typical crystallinity. ·;

The lower limit of the ethylene content is not decisive. However, copolymers are preferred which at least

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Contains 5 moles of ethylene. The α-olefin content of the amorphous Copolymers can be between a minimum of 5 mol- # and a maximum of 95 MoI-Ji.

The diene content in the copolymer is preferably between 0.1 and 20 mol. This upper limit can be exceeded, but it is not expedient, in particular for economic reasons, to introduce the polyenes into the copolymer in amounts of more than 20%. If, however, amorphous, binary copolymers of ethylene with an alkenylcyclobutene are desired, the proportion of the latter k must be above 25 mol-jS.

example 1

The reaction apparatus consists of a glass cylinder of 5 * 5 cm diameter and 700 ml capacity, the is provided with a stirrer and gas inlet and outlet pipes. The gas inlet pipe is down to the floor of the vessel and runs into a 5 * 5 cm frit Diameter.

In the kept at a constant temperature of -20 ° C reactor 200 ml of anhydrous n-heptane and 0.75 nil ■ 5-methyl-4- (4-pentenyl) cyclobutene introduced. By the A gaseous mixture of propylene and ethylene in a molar ratio of 1: 1 is introduced into the gas inlet pipe and in an amount of 250 Nl / h. circulated.

The catalyst is prepared in a 100 ml flask by reacting 0.5 millimoles of vanadyl trichloride and 2.5 millimoles of aluminum ethyl sesquichloride (1 / 2Al ₂ (C ₂ H ₅ ) ^ Cl ₃ ) in 50 ml of anhydrous n-heptane "under nitrogen · The catalyst produced in this way is forced into the reactor with nitrogen.

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The ethylene-propylene mixture is continuously in a Amount of 250 Nl / h. fed and discharged. 4 minutes after the addition of the catalyst, the reaction is terminated by adding 10 ml of methanol, which is 0.1 g Contains phenyl-ß-naphthylamine. The product comes in one Separating funnel by repeated treatment with dilute hydrochloric acid and then cleaned with water and coagulated with acetone. After drying under reduced pressure,

the 5 g of a solid product obtained which is X-ray amorphous is what an unvulcanized elastomer looks like and is completely soluble in boiling n-heptane. Infrared analysis reveals the presence of vinyl groups (band at 6.1, 10 and 11 u). The ethylene / propylene molar ratio is about 1.

100 parts by weight of the terpolymer are placed in a laboratory roller mixer with 50 parts of HAF carbon black, 5 parts of zinc oxide, 1.5 parts of sulfur, 1.5 parts of tetramethylthiuram monosulfide and 0.5 part of mercaptobenzthiazo1 mixed. The mixture is in a press for 60 minutes at 150 ° C vulcanized. A vulcanized sheet with the following properties is obtained:

Tensile strength 197 kg / cm

Elongation at break ¹ K) O %

2 module at 200 % elongation 6? kg / cm

Module at 500 # elongation 113 kg / cm

Deformation rest 10 %

Example 2

A similar reaction apparatus as in Example 1, however with a glass cylinder with a diameter of 7 * 5 cjn and a volume of 1500 ml is used in the kept at a constant temperature of -20 ° C, 700 ml of anhydrous n-heptane and 2.5 ml of 3-methyl-4-

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BATH ORIGINAL

(4-pentenyl) cyclobutene given. Through the gas inlet tube a propylene / ethylene mixture in a molar ratio of 4: 1 is introduced and in an amount of 500 standard l / hour. circulated.

In a 100 ml flask the catalyst at -20 ⁰ C by reaction of 1 millimole of vanadium tetrachloride and 5 millimoles Aluminiumäthylsesquichlorid (1/2 Al ₂ (C ₂ H ₅ prepared UCl ₃₎ in 50 ml of anhydrous n-heptane, under nitrogen. This catalyst is forced into the reactor with nitrogen.

The gaseous ethylene / propylene mixture is in an amount of 50Ό Nl / hour. continuously fed and discharged. The reaction is stopped 4 minutes after the introduction of the catalyst by adding 10 ml of methanol containing 0.1 g of phenyl-β-napthylamine. The product is purified and isolated in the manner described in Example 1. After drying under reduced pressure, 9 * 5 g of a solid product are obtained which is X-ray amorphous, looks like an unvulcanized elastomer and is completely soluble in boiling n-heptane. Infrared analysis reveals the presence of vinyl groups (bands at 6.1, 10 and Hu). The ethylene / propylene molar ratio is about 1.

The terpolymer is made in the same mixture and under the same conditions as described in Example 1, vulcanized. A vulcanized sheet with the following properties is obtained:

Tensile strength I86 kg / cm ²

Elongation at break 530 %

Module at 200 % elongation 84 kg / cm

Module at 300 · $ elongation 164 kg / cm

Deformation rest 6 %

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Example 3

In the manner described in Example 2 and held at a constant temperature of -20 ⁰ C reaction apparatus 1050 ml of anhydrous n-heptane and 3 * 5 nil 3-methyl-4- (4-pentenyl) cyclobuten added. A mixture of propylene and ethylene in a molar ratio of 4: 1 is introduced through the gas inlet pipe and in an amount of 750 standard l / hour. circulated.

The catalyst is placed in a 100 ml flask at -20 ° C under nitrogen by reacting 2.5 millimoles of vanadium tetrachloride and 7.5 millimoles of aluminum ethyl sesquichloride made in 50 ml of anhydrous n-heptane. The catalyst formed is fed into the reactor with nitrogen pressed. The gaseous ethylene / propylene mixture is in an amount of 750 Nl / hour. continuously fed and discharged.

The reaction is started 10 minutes after the introduction of the catalyst by adding 10 ml of ethanol and 0.1 g of phenylß-naphthylamine contains, canceled. The product is purified in the manner described in Example 1 and isolated. After drying under reduced pressure, 13> 7 g of a solid product are obtained which is X-ray amorphous is what a vulcanized elastomer looks like and is completely soluble in boiling n-heptane. the Infrared analysis reveals the presence of vinyl groups (bands at 6.1, 10 and 11 u). The ethylene / propylene molar ratio is about 1.,

The terpolymer is in the same blend and under the same conditions as in Example 1 at 150 ° C; vulcanized with different vulcanization times. the Vulcanizates have the following properties:

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Time (minutes) 6O 90 120 24o

Tensile strength, kg / cm ² l8o I85 178 176 Elongation at break, % 3K0 ~ 5J> 0 320 280

Module at 200 % elongation, kg / cm ² 82 90 95 99 Module at 300 $ ■ elongation, kg / cm ² 154 166 I70 deformation rest, % 6 6 6 4

Example 4

1050 ml of anhydrous n-heptane are placed in the reaction apparatus described in Example 2 and kept at -20 ° C and 1.5 ml of 3- (5-hexenyl) -cyclobutene added. By the A mixture of propylene and ethylene in a molar ratio of 4: 1 is introduced into the gas inlet tube and in one Amount of 750 Nl / h. circulated.

The catalyst is formed in a 100 ml flask by reacting 1 millimole of vanadium tetrachloride and 5 milliraoles of ethylaluminum sesquichloride (1/2 AlpppH ^ -zCT ^) in JQ ml of anhydrous n-heptane at -20 ° C under nitrogen. The catalyst formed in this way is forced into the reactor with nitrogen.

. The Ä'thylen / propylene mixture is continuously in a Amount of 750 Nl / h. fed and discharged. The reaction will 10 minutes after dr-? Introduction of the catalyst terminated by adding 10 x methanol, which contains 0.1 g of phenyl-ß-napthyla- η. The product will Purified and isolated in the manner described in Example 1. After drying under reduced pressure 16 g of a product obtained which is X-ray amorphous, looks like an unvulcanized elastomer and is completely soluble in boiling n-heptane. The infrared. analysis reveals the presence of vinyl bonds (bands at 6.1, 10 and Hu). The ethylene / propylene molar ratio is about 1. ~

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- 15 -

The terpolymer is in the same blend and under vulcanized under the same conditions as in Example 1. A vulcanized sheet with the following properties will get:

Tensile strength 178 kg / cm ²

Elongation at break _v 360 %

Module at 200 % elongation 75 kg / cm

* 2 module at] 500 # elongation 146 kg / cm

Deformation rest 8 %

Example 5

Similar in a reaction apparatus kept at -20 ° C that described in Example 1, 200 ml of anhydrous n-heptane and 1 ml of J5 (l-methylallyl) -cyclobutene are introduced. A gaseous mixture of propylene and ethylene in a molar ratio of 2: 1 is introduced through the gas introduction tube and in an amount of 450 Nl / hour. circulated.

The catalyst is prepared in a 100 mL flask to be implemented in the 2.8 millimoles and 14 millimoles Vanadintriacetylacetonat Aluminiumdiäthylmonochlorid in JO ml of anhydrous toluene at -20 ⁰ C under nitrogen. The catalyst formed in this way is forced into the reactor with nitrogen.

The gaseous ethylene / propylene mixture is continuously in an amount of 450 Nl / hour. fed and discharged. The reaction is 2.5 minutes after the introduction of the catalyst by adding 10 ml of methanol, the 0.1 g phenyl-ß-naphthylamine, canceled. That The product is purified and isolated in the manner described in Example 1. After drying under reduced 4.5 g of a solid product are obtained under pressure, which is X-ray amorphous, like an unvulcanized elastomer

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meres looks and is completely soluble in boiling n-heptane. The infrared spectrum shows the presence of Vinyl groups (bands at 10 and 1Iu) ... The ethylene / propylene molar ratio is about 1.

The copolymer is vulcanized in the same mixture and under the same conditions as in Example 1. A vulcanized sheet with the following properties is obtained:

Tensile strength 190 kg / cm

Elongation at break

) % Elongation 65 kg / cr

Modulus at J500 % elongation 150 kg / cm ^£

Deformation rest 10 %

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Claims (8)

Claims 1) Vulcanizable, essentially linear, amorphous, high molecular weight copolymers of ethylene and / or one or more aliphatic'α-olefins of the general formula R-CH = CH ₂ , in which R is an alkyl group with 1 to 6 carbon atoms, and one or more monoalkenyl cyclobutenes, these copolymers consisting essentially of unsaturated macromolecules with units from each monomer used. 2) copolymers according to claim 1, containing monomer units of ethylene, propylene and / or butene-1 and of 3-methyl-4- (4-pentenyl) -eyclobutene, 3- (5-hexenyl) -cyclobutene and / or 3- (l-methylallyl) -cyclobutene. y) Vulcanized elastomers made from the copolymers according to Claim 1 or 2. 4) Process for the preparation of products according to claim 1 to j5, characterized in that the monomers in Presence of catalysts made from vanadium compounds and organometallic compounds of aluminum or Berylliums have been obtained, at least one the constituents contain halogen atoms, copolymerized and the essentially linear, amorphous, high molecular weight copolymers optionally vulcanized. 5) The method of claim K, characterized in that one carries out the copolymerization at temperatures ranging between -8o ° and 125 ⁰ C. 0Q9820 / 16S1 originally inspected 6) Process according to claim 4 and 5 * characterized in that the copolymerization is carried out at temperatures in the range between 0 ° and -8o ° C, preferably between -10 ° and
-50 ⁰ C, performs. 7) Method according to claim 4 to 6, characterized in that that in the copolymerization of monoalkenylcyclobutenes with ethylene and propylene at a molar ratio between ethylene and propylene in the liquid phase of less than or at most 1: 4 works. 8) Process according to claim 4 to 6, characterized in that in the copolymerization of monoalkenylcyclobutenes with ethylene and butene-1 at a molar ratio
between ethylene and butene-1 in the liquid phase of
works below or at most 1:20. 009820/1861